Alkoxy menthene-7-carbinols and process of preparing same



Patented Aug. 5, 1947 V ALKOXY MENTHENE-I-CARBENOLS AND PRGCESS F PREPARING SAME Joseph P. Bain and Albert E. Best, Jacksonville,

Fla", assignors to The Giidden Sompany, illeveland, Ohio, a corporation of Ohio No Drawing. Application Qctohei- 4, 1946, Serial No. 701,090

11 Glaims. (Cl. 260-489) 2 This invention relates to the preparation of new means for producing alkoxy monocyclic alcohols alcohol compositions and more particularly to the and the esters thereof. alkoxy monocyclic alcohols prepared from dicyclic Another object of our invention is to afiord primary alcohols having the empirical formula means for the production of alkoxy menthene-7- CIIHISO. These compounds may alternatively be carbinols and the esters thereof.

described as alkyl ethers of primary monocyclic It is a further object of our invention to proalcohols, possessing the empirical formula vide a new series of ether-alcohols and the esters C11H19O2R thereof Still another object of our invention is to prowhere R is an alkyl radical. This application is m vide a. process for the preparation of alkoxy ala continuation-in-pa t o 0 Imp applicacoliols, and esters of the class described, from an tion Serial N0. 5 3 filed March 18, 19 unsaturated ibicyclic primary monohydric alcohol United States Patent No. 2,340,294 discloses an of empirical formula 01 1-1180.

alcoh l for d y re -D P Yet another object of our invention is to pronene with anhydrous formaldehyde to produce an d alkoxy menthene l-carbinols,

alcohol having th empirical formula Cal-I180, Other objects and a fuller understanding of which is a bicyclic primary unsaturated alcohol. the present invention will be afiorded by refer- Since this alcohol is prepared from nopinene, it nc to the following examples: is called nopol, and is believed to have the 01- Example NO 1 lowing structure:

Five hundred parts of nopol were taken, possessing the following characteristics:

EC CH CH Density at 0 .966 Refractive index ((1 1.4895

25 Optical rotation (10 cm. tube, sodium H light) 35.7'7 This quantity was dissolved in one thousand parts of methanol, and treated with a solution of 30 ten parts of boron fluoride in two hundred parts It has been found that nopol reacts with alcoof methanol. The mixture was refluxed for three hols in the presence oi acidic catalysts to form hours, and water was then added. A portion of alkoxy menthene-7=carbinols. By analogy to the the reaction product was washed with water to addition of water to alpha-pinene, the alkoxy remove the methanol and the catalyst, and then group probably is attached to the 8 carbon atom fractionated at 10 mm. pressure. The fractionaof the menthene nucleus, and the products of tion gave the following results: these reactions probably possess the structure:

o-cm-ornon Fraction Weight H5O CH 30 mo cm g3 on 92 OR 214 HaC CH: 5 5 Residue The acidic catalysts employed are boron fluoride, sulphuric acid, and in general, acidic catalysts oi the type disclosed by Evans and Edlund Fractions No. 2 and No. 3- consisted of menthain the "Journal of Industrial and Engineering 60 diene-7-carbinols formed byisomerizationof the Chemistry, vol. 28, p. 1186, 1936. bicyclic structure of nopol. Fractions No. 6 and V The ethers of the present invention are useful No. 7 consisted of a substanti'allypure 'unsatu- V as plasticizers for plastic compositions, and their rated methyl ether of empirical formula C12H22O2. esters are useful as high boiling plasticizers. The product contains one hydroxyl group per It is an object of our invention to provide a molecule.

Example No. 2

Nopol (500 parts) was dissolved in ethanol (1000 parts) and treated with a solution of 10 parts of boron fluoride in 200 parts of ethanol. This mixture was refluxed for five hours, after which the acid catalyst and the excess ethanol were removed by washing with water. The separated reaction product was then fractionated, the distillation being carried out at 10 mm. pressure. A yield was obtained of about 127 parts of an unsaturated ethyl ether, containing one hydroxyl group per molecule, and having the empirical formula CraHnOz. This product possessed the following physical characteristics:

B. P. at 10 mm C 152-163 Refractive index (Ne 1.48 Optical rotation (10 cm. tube, sodium light) -55 to -60 Example No. 3

by using the corresponding carboxylic acids, and

esterifying in the usual manner. examples are illustrative:

Example No. 4

1 mole of acetic anhydride (102 gm.) Was heated to about 70 C. together with 1 gram of sodium acetate. One mole of methoxy-menthene-(l) -'lcarbinol was added slowly, heated of reaction increased the temperature to 124 C. After adding all of the alcohol, the mixture was refluxed at 150-160 C. for several hours. After the acetic acid was removed from the ester by washing, the ester was fractionated at 10 mm. pressure and boiled 157-158" C. It possessed a refractive index at 25 of 1.4715 and had saponification number 222.5.

Example No. 5

74 gm. of phthalic anhydride was heated with 198 gm. methoxy-menthene-(l)-7-carbinol for 2 hours at about 200 C. Unreacted materials were removed at mm. pressure leaving a viscous residue possessing an acid number of 40.2 and saponiiication number 145.

Example No. 6

49 gm. of maleic anhydride was heated with 198 gm. methoxy-menthene-(l)-7-oarbinol at about 200 C. for 2 hours after which unreacted materials were stripped out at 10 mm. pressure, leaving a residue of acid number 48, saponification number 184.

Example No. 7

Molar quantities of 2-ethyl hexoicacid and methoxy-menthene-(l)-7-carbino1 were heated at 180 C. for several hours and then unreacted materials were stripped out at 10 mm. pressure The following 4 leaving a residue of 2-ethyl hexoate of methoxymenthene-( 1) -7-carbinoi possessing an acid number of 1.

It is believed that the reactions producing these fibers may be represented by the following equaons:

C-CHr-CHaOH no/\on C-CHz-CHsOH Although we have described our invention with a certain degree of particularity, it is understood that the present disclosure has been made only by way of example, and that numerou changes may be made in the details of operation without departing from the spirit and scope of the invention as hereinafter claimed.

What w claim is:

l. The process which comprises heating 7- methylol A -pinene with an alcohol in the presence of an acidic catalyst at temperatures sufilcient to cause reflux distillation of the alcohol and to form the aikoxy primary unsaturated monocyclic monohydric alcohol.

2. The process which comprises heating 7- methylol A -plnene with methanol in the presence of an acidic catalyst at temperatures sufilcient to cause reflux distillation of the methanol to form the methoxy primary unsaturated monocyclic monohydric alcohol.

3. The process which comprises heating 7- methylol A -pinene with ethanol in the presence of an acidic catalyst at temperatures sumcient tocause reflux distillation of the ethanol to form the ethoxy primary unsaturated monocyclic monohydric alcohol.

4. 8-alkoxy-menthene- (l) -7-carbinols.

5. As a new composition of matter, B-methoxymenthene (1) -7-carbin0l.

6. As a new composition of matter, 8-ethoxymenthene (1)-7-carbinol.

7. As new compositions of matter, substances of the class consisting of the S-alkoxy-menthene (1) -'l-carbinols, and the carboxylic acid esters thereof.

8. Carboxylic acid esters of the alkoxy alcohols of claim 4.

9. Alkyl carboxylic acid esters of the alkoxy alcohols of claim 4.

10. The acetic acid esters of the alkoxy alcohols of claim 4.

11. The acetic acid ester of 8-methoxy-menthene (1)-7-carbinol.

JOSEPH P. BAIN. ALBERT H. BEST. 

